Silicon-containing layer deposition with silicon compounds

ABSTRACT

Methods for depositing a silicon-containing film are described. The methods may include delivering a silicon compound to a surface or a substrate, and reacting the silicon compound to grow the silicon-containing film. The silicon compound may be one or more compounds having a formula selected from the group Si 4 X 8 , Si 4 X 10 , Si 5 X 10 , and Si 5 X 12 , where X is independently a hydrogen or halogen.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. Ser. No. 10/688,797, filed Oct. 17, 2003, which claims benefit of U.S. Ser. No. 60/419,376, filed Oct. 18, 2002, U.S. Ser. No. 60/419,426, filed Oct. 18, 2002, and U.S. Ser. No. 60/419,504, filed Oct. 18, 2002, which are herein incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the invention generally relate to deposition of silicon-containing films, and more particularly to silicon compound compositions and related processes to deposit silicon-containing films.

2. Description of the Related Art

Atomic layer epitaxy (ALE) offers meticulous control of film thickness by growing single atomic layers upon a crystal lattice. ALE is employed to develop many group IV semiconductor materials, such as silicon, germanium, silicon germanium, silicon carbon and silicon germanium carbon. Silicon based materials, produced via ALE, are of interest for use as semiconductor materials. The silicon based materials can include germanium and/or carbon at selectable concentrations and are grown as polysilicon, amorphous or monocrystalline films. Silicon-ALE, in which a silicon-containing film is epitaxial grown, consists of two steps.

A monolayer of partially decomposed source gas molecules (e.g., SiH4 or SiH2Cl2) is adsorbed over the substrate or surface. The adsorbate may consists of a silicon atom and at least another kind of atom or group bonded with silicon, such as chlorine, hydrogen or methyl (e.g., SiCln, SiHn or H4-nSiMen, where n=1-4). The adsorbate decomposes to form adatoms of silicon on the surface. The adatoms migrate or diffuse on the surface to an empty lattice site of the silicon crystal. The crystal continues to form and grow as adatoms are generated on the crystalline surface and incorporated into the lattice. By-product removal is achieved and a new surface is created on the monolayer. The monolayer growth in the next cycle is made possible.

Source gases used during silicon deposition include lower silanes (e.g., silane, dichlorosilane and tetrachlorosilane) as well as higher silanes (e.g., disilane, hexachlorodisilane and trisilane). Silane and dichlorosilane are the most common source gases used during Si-ALE, such as described in U.S. Ser. No. 09/963,411, published as U.S. Pub. No. 2002-0052077, and issued as U.S. Pat. No. 6,384,437. These lower silanes require the substrate to be maintained at high temperatures, often in the range of 800-1,000° C. Higher silanes are utilized as source gases to lower the temperature needed during Si-ALE. Disilane is used to grow silicon by ultraviolet-photostimulated ALE in the temperature range of 180-400° C., as demonstrated by Suda, et al., J. Vac. Sci. Technol. A, 8 (1990) 61, as well as by Lubben, et al., J. Vac. Sci. Technol. A, 9 (1991) 3003. Furthermore, trisilane is used as a source gas during Si-ALE at about 380° C., as reported by Imai, et al., Jpn. J. Appl. Phys., 30 (1991) 3646.

Si-ALE with supplemental etchants has also been realized. Horita, et al., U.S. Ser. No. 09/991,959, published as U.S. Pub. No. 2002-0127841, and issued as U.S. Pat. No. 6,503,799, teaches the combination of dichlorosilane and hydrogen chloride to accomplish selective silicon growth. Supplemental etchants are generally halogenated and/or radical compounds (e.g., HCl or .Cl) that necessitate high reactivity. Therefore, hazardous and toxic conditions are often associated with etchant use.

Therefore, there is a need to provide silicon-containing compounds that provide both a source chemical for silicon deposition and a source chemical as an etchant. The silicon-containing compounds should be versatile to be applied in a variety of silicon depos

BRIEF SUMMARY OF THE INVENTION

In one embodiment, the invention generally provides a method for depositing a silicon-containing film, comprising delivering a silicon compound to a substrate surface and reacting the silicon compound to deposit the silicon-containing film on the substrate surface. The silicon compound comprises a structure:

wherein X₁-X₆ are independently hydrogen or halogen, R is carbon, silicon or germanium and X₁-X₆ comprise at least one hydrogen and at least one halogen.

In another embodiment, the invention generally provides a composition of matter comprising a structure:

wherein X₁-X₆ are independently hydrogen or halogen, R is carbon, silicon or germanium and X₁-X₆ comprise at least one hydrogen and at least one halogen and the proviso that R is not carbon when X₄, X₅ and X₆ are fluorine.

In another embodiment, the invention generally provides a composition of matter comprising a structure:

wherein X₁-X₆ are independently hydrogen or halogen and R is germanium.

In another embodiment, the invention generally provides a method for depositing a silicon-containing film, comprising delivering a silicon compound to a substrate surface and reacting the silicon compound to deposit the silicon-containing film on the substrate surface. The silicon compound comprising structures:

wherein X₁-X₈ are independently hydrogen or halogen, R is carbon, silicon or germanium and X₁-X₈ comprise at least one halogen.

In another embodiment, the invention generally provides a composition of matter comprising structures:

wherein X₁-X₈ are independently hydrogen or halogen, R is carbon, silicon or germanium and X₁-X₈ comprise at least one halogen.

In another embodiment, the invention generally provides a composition of matter comprising structures:

wherein X₁-X₈ are independently hydrogen or halogen and R is germanium.

In another embodiment, the invention generally provides a method for depositing a silicon-containing film by delivering a silicon compound to a substrate surface and reacting the silicon compound to deposit the silicon-containing film on the substrate surface. In some embodiments, the silicon compound comprises three silicon atoms, fourth atom of carbon, silicon or germanium and atoms of hydrogen or halogen with at least one halogen. In other embodiments, the silicon compound comprises four silicon atoms, fifth atom of carbon, silicon or germanium and atoms of hydrogen or halogen with at least one halogen. In some embodiments, the silicon-containing film is selected from the group consisting of silicon, silicon germanium, silicon carbon and silicon germanium carbon.

In another embodiment, the invention generally provides a composition of matter comprising three silicon atoms, fourth atom of carbon, silicon or germanium and atoms of hydrogen or halogen with at least one halogen. In other embodiments, the invention generally provides a composition of matter comprising four silicon atoms, fifth atom of carbon, silicon or germanium and atoms of hydrogen and/or halogen.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the invention pertain to processes for epitaxially depositing silicon-containing films of a desired thickness on a substrate. The processes generally include silicon compounds that contain silicon sources, as well as etchant sources, within the same molecule. A silicon source is a compound that includes from at least one silicon atom and to five silicon atoms. An etchant source is a compound that includes at least one functional group with etchant characteristics. In some embodiments, molecules are used that also contain silicon germanium sources or silicon carbon sources.

In one aspect, embodiments of the invention relate to silicon compounds comprising a structure:

wherein X₁-X₆ are independently hydrogen or halogen, R is carbon, silicon or germanium and X₁-X₆ comprise at least one hydrogen and at least one halogen.

Silicon sources have formulas such as Cl₃SiSiCl₂H, Cl₃SiSiClH₂, Cl₃SiSiH₃, HCl₂SiSiH₃, H₂ClSiSiH₃, HCl₂SiSiCl₂H and H₂ClSiSiClH₂. Other silicon sources are derived by the replacement of at least one H-atom and/or at least one Cl-atom with another halogen, such as fluorine. Therefore, silicon sources may have chemical formulas such as Cl₃SiSiF₂H, F₃SiSiClH₂, F₃SiSiH₃, F₃SiSiCl₃, HFClSiSiF₃, H₂ClSiSiH₃, FCl₂SiSiF₂H and H₂ClSiSiClF₂. Other similarly halogenated silicon sources enable the processes.

Silicon germanium sources may have formulas such as Cl₃SiGeCl₃, H₃SiGeH₃, Cl₃SiGeCl₂H, Cl₃SiGeClH₂, Cl₃SiGeH₃, HCl₂SiGeH₃, H₂ClSiGeH₃, HCl₂SiGeCl₂H, H₂ClSiGeClH₂, Cl₃GeSiCl₂H, Cl₃GeSiClH₂, Cl₃GeSiH₃, HCl₂GeSiH₃, H₂ClGeSiH₃, HCl₂GeSiCl₂H and H₂ClGeSiClH₂. Other silicon germanium sources are derived by the replacement of at least one H-atom and/or at least one Cl-atom with another halogen, such as fluorine. Therefore, silicon germanium sources may have chemical formulas such as F₃SiGeCl₃, F₃SiGeH₃, F₃GeSi₃, F₃GeSiH₃, H₃SiGeCl₃, H₃SiGeHCl₂, F₃SiGeCl₂H, F₃SiGeClH₂, HCl₂SiGeH₃, H₂ClSiGeF₃, FCl₂SiGeCl₂H, H₂ClSiGeClH₂, F₃GeSiCl₂H, F₃GeSiClH₂ and H₂FGeSiClH₂. Other similarly halogenated silicon germanium sources enable the processes.

Silicon carbon sources may have formulas such as H₃SiCH₃, Cl₃SiCCl₃, Cl₃SiCCl₂H, Cl₃SiCClH₂, Cl₃SiCH₃, HCl₂SiCH₃, H₂ClSiCH₃, HCl₂SiCCl₂H, H₂ClSiCClH₂, Cl₃CSiCl₂H, Cl₃CSiClH₂, Cl₃CSiH₃, HCl₂CSiH₃, H₂ClCSiH₃, HCl₂CSiCl₂H and H₂CiCSiClH₂. Other silicon carbon sources are derived by the replacement of at least one H-atom and/or at least one Cl-atom with another halogen, such as fluorine. Therefore, silicon carbon sources may have chemical formulas such as Cl₃SiCF₂H, Cl₃SiCFH₂, F₃SiCH₃, FCl₂SiCH₃, H₂FSiCH₃, FCl₂SiCCl₂H, FH₂ClSiCClH₂, FCl₃CSiCl₂H, Cl₃CSiClHF, F₃CSiH₃, F₃CSiCl₃, H₃CSiF₃, Cl₃CSiF₃, FCl₂CSiH₃, H₂FCSiH₃, FCl₂CSiCl₂H and H₂ClCSiFH₂. Other similarly halogenated silicon carbon sources enable the processes.

Silicon compounds may be used to deposit a silicon motif (e.g., Si—R, where R is silicon, germanium or carbon) contained within the molecule. The hydrogens and/or halogens are ligands that are removed from the molecule as the silicon motif is reduced and deposited. The deposition forms a silicon-containing film during the procedure. The ligands may form an in-situ etchant from the liberated hydrogen and/or halogen. The in-situ etchants include H, H₂, HX, X, X₂ and XX′, where X and X′ are different, but both halogen, as well as other combinations of hydrogen and halogen molecules including radical or ionic species (e.g., .H or .X). Herein, the word halogen includes fluorine, chlorine, bromine, iodine, radicals thereof, ions thereof and combinations thereof.

In another aspect, embodiments of the invention relate to silicon compound comprising structures:

wherein X₁-X₈ are independently hydrogen or halogen, R is carbon, silicon or germanium and X₁-X₈ comprise at least one halogen. In some embodiments, the silicon-containing film is selected from the group consisting of silicon, silicon germanium, silicon carbon and silicon germanium carbon.

Other silicon compounds are used to deposit a silicon motif (e.g., Si—Si—R or Si—R—Si, where R is silicon, germanium or carbon) contained within the molecule. Silicon sources may have formulas such as H₃SiSiH₂SiH₂Cl, H₃SiSiH₂SiHCl₂, H₃SiSiH₂SiCl₃, H₃SiSiHClSiH₂Cl, H₃SiSiHClSiHCl₂, H₃SiSiHClSiCl₃, H₃SiSiCl₂SiH₂Cl, H₃SiSiCl₂SiHCl₂, H₃SiSiCl₂SiCl₃, HCl₂SiSiH₂SiH₂Cl, HCl₂SiSiH₂SiHCl₂, Cl₃SiSiH₂SiCl₃, HCl₂SiSiCl₂SiH₂Cl, H₂ClSiSiHClSiHCl₂, Cl₃SiSiH₂SiCl₃, Cl₃SiSiHClSiCl₃, HCl₂SiSiCl₂SiHCl₂ and H₃SiSiCl₂SiH₃. Other silicon sources are derived by the replacement of at least one H-atom and/or at least one Cl-atom with another halogen, such as fluorine. Therefore, silicon sources may have formulas such as F₃SiSiH₂SiH₃, F₃SiSiH₂SiCl₃, H₃SiSiH₂SiH₂F, H₃SiSiH₂SiHF₂, H₃SiSiH₂SiF₃, H₃SiSiHFSiH₂Cl, F₃SiSiHClSiHF₂, H₃SiSiFHSiCl₃, H₃SiSiF₂SiH₂F, H₃SiSiCl₂SiFCl₂ and H₃SiSiF₂SiCl₃. Other similarly halogenated silicon sources enable the processes. Furthermore, cyclic-trisilane and cyclic-halotrisilane are used within the scope of the invention.

Silicon germanium sources may have formulas such as H₃SiSiH₂GeH₂Cl, H₃SiSiH₂GeH₃, H₃SiSiH₂GeHCl₂, H₃SiSiH₂GeCl₃, H₃SiSiHClGeH₂Cl, H₃SiSiHClGeHCl₂, H₃SiGeHClSiCl₃, H₃SiGeCl₂SiH₂Cl, H₃SiGeCl₂SiHCl₂, H₃SiGeCl₂SiCl₃, HCl₂SiGeH₂SiH₂Cl, HCl₂SiSiH₂GeHCl₂, Cl₃SiSiH₂GeCl₃, HCl₂SiGeCl₂SiH₂Cl, H₂ClSiGeHClSiHCl₂, Cl₃SiGeH₂SiCl₃, Cl₃SiSiHClGeCl₃, HCl₂SiGeCl₂SiH₃ and H₃GeSiCl₂SiH₃. Other silicon germanium sources are derived by the replacement of at least one H-atom and/or at least one Cl-atom with another halogen, such as fluorine. Therefore, silicon germanium sources have formulas such as F₃SiSiH₂GeH₃, F₃SiSiH₂GeCl₃, F₃GeSiH₂SiH₃, F₃GeSiH₂SiCl₃, F₃SiGeH₂SiH₃, F₃SiGeH₂SiCl₃, F₃SiSiH₂GeCl₂H, H₃SiSiF₂GeH₂Cl, F₃SiSiH₂GeHCl₂, H₃SiSiF₂GeCl₃, H₃SiSiCl₂GeH₂Cl, H₃SiSiHClGeHF₂, H₃SiGeH₂SiCl₃, H₃SiGeCl₂SiH₂Cl, F₃SiGeCl₂SiHCl₂, H₃SiGeF₂SiCl₃. Other similarly halogenated silicon germanium sources enable the processes. Furthermore, cyclic germaniumsilanes and cyclic-halogermaniumsilanes are used within the scope of the invention.

Silicon carbon sources may have formulas such as H₃SiSiH₂CH₂Cl, H₃SiSiH₂CHCl₂, H₃SiSiH₂CCl₃, H₃SiSiHClCH₂Cl, H₃SiSiHClCHCl₂, H₃SiCHClSiCl₃, H₃SiCCl₂SiH₂Cl, H₃SiCCl₂SiHCl₂, H₃SiCCl₂SiCl₃, HCl₂SiCH₂SiH₂Cl, HCl₂SiSiH₂CHCl₂, Cl₃SiSiH₂CCl₃, HCl₂SiCCl₂SiH₂Cl, H₂ClSiCHClSiHCl₂, Cl₃SiCH₂SiCl₃, Cl₃SiSiHClCCl₃, HCl₂SiCCl₂SiH₃ and H₃CSiCl₂SiH₃. Other silicon carbon sources are derived by the replacement of at least one H-atom and/or at least one Cl-atom with another halogen, such as fluorine. Therefore, silicon carbon sources have formulas such as F₃SiSiH₂CH₃, F₃SiSiH₂CCl₃, F₃CSiH₂SiH₃, F₃CSiH₂SiCl₃, F₃SiCH₂SiH₃, F₃SiCH₂SiCl₃, F₃SiSiH₂CCl₂H, H₃SiSiF₂CH₂Cl, F₃SiSiH₂CHCl₂, H₃SiSiF₂CCl₃, H₃SiSiHFCH₂Cl, H₃SiSiHClCHF₂, H₃SiCHFSiCl₃, H₃SiCCl₂SiH₂F, F₃SiCCl₂SiHCl₂, H₃SiCF₂SiCl₃. Other similarly halogenated silicon carbon sources enable the processes. Furthermore, cyclic-carbosilanes and cyclic-halocarbosilanes are used within the scope of the invention.

In another aspect, embodiments of the invention relate to silicon compounds, compounds 1-8, having the following representative structures:

where X₁-X₁₀ are independently hydrogen or halogen, such as fluorine, chlorine, bromine or iodine and R is carbon, silicon or germanium.

In another aspect, embodiments of the invention relate to silicon compounds, compounds 9-32, having the following representative structures:

where X₁-X₁₂ are independently hydrogen or halogen, such as fluorine, chlorine, bromine or iodine and R is carbon, silicon or germanium. The structures of compounds 1-32 are representative and do not imply a particular isomer. Herein, any elemental name or chemical symbol anticipates the use of the respective elemental isotopes, such as the use of hydrogen (¹H or H) also includes the use of deuterium (²H or D) and tritium (³H or T).

Therefore, silicon compounds may be used to deposit a silicon motif (e.g., Si₃R or Si₄R, where R is silicon, germanium or carbon) contained within the molecule. The silicon motif of compounds 1-8 is represented by Si₃R and the silicon motif of compounds 9-32 is represented by Si₄R. The hydrogens and/or halogens are ligands that are removed from the molecule as the silicon motif is reduced and deposited. The deposition forms a silicon-containing film during the deposition process.

Silicon sources may include compounds with the formulas Si₄X₈, Si₄X₁₀, Si₅X₁₀ and Si₅X₁₂, where X is independently hydrogen or halogen. Silicon sources containing hydrogen and/or chlorine may include compounds with the formulas Si₄H_(8−n)Cl_(n), Si₄H_(10−m)Cl_(m), Si₅H_(10−p)Cl_(p) and Si₅H_(12−q)Cl_(q), where n=1-8, m=1-10, p=1-10 and q=1-12. Silicon sources may include Si₄H₉Cl, Si₄H₈Cl₂, Si₄H₇Cl₃, Si₄H₆Cl₄, Si₄H₅Cl₅, Si₄H₄Cl₆, Si₄H₃Cl₇, Si₄H₂Cl₈, Si₄HCl₉, Si₄Cl₁₀, Si₅H₁₁Cl, Si₅H₁₀Cl₂, Si₅H₉Cl₃, Si₅H₈Cl₄, Si₅H₇Cl₅, Si₅H₆Cl₆, Si₅H₅Cl₇, Si₅H₄Cl₈, Si₅H₃Cl₉, Si₅H₂Cl₁₀, Si₅HCl₁₁ and Si₅Cl₁₂. Other silicon sources are derived by the replacement of at least one Cl-atom with another halogen, such as fluorine, bromine or iodine and enable the processes. In one example, isotetrasilane, (SiH₃)₃SiH, is a silicon source compound. In another example, neopentasilane, (SiH₃)₄Si, is a silicon source compound. Furthermore, cyclic-tetrasilane, cyclic-halotetrasilane, cyclic-pentasilane and cyclic-halopentasilane are used within the scope of the invention.

Silicon germanium sources may include compounds with the formulas Si₃GeX₈, Si₃GeX₁₀, Si₄GeX₁₀ and Si₄GeX₁₂, where X is independently hydrogen or halogen. Silicon germanium sources containing hydrogen and/or chlorine may include compounds with the formulas Si₃GeH_(8−n)Cl_(n), Si₃GeH_(10−m)Cl_(m), Si₄GeH_(10−p)Cl_(p) and Si₄GeH_(12−q)Cl_(q), where n=1-8, m=1-10, p=1-10 and q=1-12. Silicon germanium sources may include Si₃GeH₉Cl, Si₃GeH₈Cl₂, Si₃GeH₇Cl₃, Si₃GeH₆Cl₄, Si₃GeH₅Cl₅, Si₃GeH₄Cl₆, Si₃GeH₃Cl₇, Si₃GeH₂Cl₈, Si₃GeHCl₉, Si₃GeCl₁₀, Si₄GeH₁₁Cl, Si₄GeH₁₀Cl₂, Si₄GeH₉Cl₃, Si₄GeH₈Cl₄, Si₄GeH₇Cl₅, Si₄GeH₆Cl₆, Si₄GeH₅Cl₇, Si₄GeH₄Cl₈, Si₄GeH₃Cl₉, Si₄GeH₂Cl₁₀, Si₄GeHCl₁₁ and Si₄GeCl₁₂. Other silicon germanium sources are derived by the replacement of at least one Cl-atom with another halogen, such as fluorine, bromine or iodine and enable the processes. Furthermore, cyclic germaniumsilanes and cyclic-halogermaniumsilanes are used within the scope of the invention.

Silicon carbon sources may include compounds with the formulas Si₃CX₈, Si₃CX₁₀, Si₄CX₁₀ and Si₄CX₁₂, where X is independently hydrogen or halogen. Silicon carbon sources containing hydrogen and/or chlorine may include compounds with the formulas Si₃CH_(8−n)Cl_(n), Si₃CH_(10−m)Cl_(m), Si₄CH_(10−p)Cl_(p) and Si₄CH_(12−q)Cl_(q), where n=1-8, m=1-10, p=1-10 and q=1-12. Silicon carbon sources may include Si₃CH₉Cl, Si₃CH₈Cl₂, Si₃CH₇Cl₃, Si₃CH₆Cl₄, Si₃CH₅Cl₅, Si₃CH₄Cl₆, Si₃CH₃Cl₇, Si₃CH₂Cl₈, Si₃CHCl₉, Si₃CCl₁₀, Si₄CH₁₁Cl, Si₄CH₁₀Cl₂, Si₄CH₉Cl₃, Si₄CH₈Cl₄, Si₄CH₇Cl₅, Si₄CH₆Cl₆, Si₄CH₅Cl₇, Si₄CH₄Cl₈, Si₄CH₃Cl₉, Si₄CH₂Cl₁₀, Si₄CHCl₁₁ and Si₄CCl₁₂. Other silicon carbon sources are derived by the replacement of at least one Cl-atom with another halogen, such as fluorine, bromine or iodine and enable the processes. Furthermore, cyclic carbonsilanes and cyclic-halocarbonsilanes are used within the scope of the invention.

Many of the silicon compounds are in the gaseous or liquid state at ambient pressure and temperature. However, during a deposition process, the silicon compounds may be in solid, liquid, gas or plasma state of matter, as well as radical or ionic. In general, the silicon compounds may be delivered to the substrate surface by a carrier gas. Carrier or purge gases may include N₂, H₂, Ar, He, forming gas and combinations thereof.

Silicon compounds may be used solely or in combination with compounds, including other silicon compounds, to deposit silicon-containing films with a variety of compositions. In one example, a silicon compound, such as Cl₃SiSiH₂SiH₂SiH₃, is used to etch the substrate surface, as well as to epitaxially grow a crystalline silicon film on the substrate. In another example, the substrate surface may need a different etchant than in the previous example. Therefore, Cl₃SiSiH₂SiCl₂SiH₂F is used in the etching process, while H₂ClSiSiH₂SiH₂SiH₃ is used in the deposition process. In another example, a silicon germanium source, such as H₃SiSiH₂SiH₂GeHCl₂, is used to continue the deposition process and to grow a silicon germanium film on the silicon film.

In another embodiment, the RF₃ fragment, where R=Si, Ge or C, can be incorporated into the molecule. The RF₃ is thermodynamically stable due to the strong R—F bond. A molecule, such as F₃CSiH₂SiH₃SiH₃, decomposes to deposit silicon-containing films, while the CF₃ fragment is generated as part of a volatile product. A silicon compound with the RF₃ fragment can have favorable properties, such as volatility (vapor pressure and boiling point).

Silicon compounds are utilized within embodiments of the processes to deposit silicon-containing films used for Bipolar (base, emitter, collector, emitter contact), BiCMOS (base, emitter, collector, emitter contact) and CMOS (channel, source/drain, source/drain extension, elevated source/drain, substrate, strained silicon, silicon on insulator, isolation, contact plug). Other embodiments of processes teach the growth of silicon-containing films that can be used as gate, base contact, collector contact, emitter contact, elevated source/drain and other uses.

Embodiments of the invention teach processes to grow selective silicon films or blanket silicon films. Selective silicon film growth generally is conducted when the substrate or surface includes more than one material, such as a crystalline silicon surface having oxide or nitride features. Usually, these features are dielectric material. Selective epitaxial growth to the crystalline, silicon surface is achieved while the feature is left bare, generally, with the utilization of an etchant (e.g., HCl). The etchant removes amorphous silicon or polysilicon growth from features quicker than the etchant removes crystalline silicon growth from the substrate, thus selective epitaxial growth is achieved. In some embodiments, selective epitaxial growth of the silicon-containing film is accomplished with the use of no etchants. During blanket silicon epitaxy, a film grows across the whole substrate regardless of particular surface features and compositions.

Embodiments of the invention teach processes to grow selective silicon films or blanket silicon films. Selective silicon film growth generally is conducted when the substrate or surface includes more than one material, such as a crystalline silicon surface having oxide or nitride features. Usually, these features are dielectric material. Selective epitaxial growth to the crystalline, silicon surface is achieved while the feature is left bare, generally, with the utilization of an etchant (e.g., HCl). The etchant removes amorphous silicon or polysilicon growth from features quicker than the etchant removes crystalline silicon growth from the substrate, thus selective epitaxial growth is achieved. In some embodiments, selective epitaxial growth of the silicon-containing film is accomplished with the use of no etchants. During blanket silicon epitaxy, a film grows across the whole substrate regardless of particular surface features and compositions.

Embodiments of the invention may use processes with an etchant source and a silicon source incorporated into the silicon compound. The deposition processes form silicon-containing films and liberate ligands from the silicon compounds. The ligands, hydrogen and/or halogen, are in-situ etchants. The in-situ etchants include H, H₂, HX, X, X₂ and XX′, where X is a halogen and X′ is a different halogen than X, as well as any other combinations of hydrogen and halogen molecules including radical or ionic species. However, supplemental etchants can also be used with the silicon compounds and are demonstrated in various embodiments of the invention. Supplemental etchants can include: CHF₃, CF₄, C₄F₈, CH₂F₂, ClF₃, Cl₂, F₂, Br₂, NF₃, HCl, HF, HBr, XeF₂, NH₄F, (NH₄)(HF₂) and SF₆. For example, H₃SiSiH₂SiH₂SiCl₂H and HCl are used during the growth of a silicon-containing film.

In some processes, silicon compounds are introduced to the heated (e.g., 500° C.) surface of a substrate and the silicon motif is deposited as the silicon-containing film. The liberated ligands of the silicon compounds are converted to an in-situ etchant. The in-situ etchants support in the growth of selective silicon epitaxy by removing amorphous silicon or polysilicon from substrate features (e.g., oxides or nitrides) at a faster rate than removing crystalline silicon from the surface. Hence, crystalline silicon grows about the substrate features.

Reducing agents may be used in various embodiments of the invention to transfer electrons between compounds. Generally, silicon compounds are reduced to elemental films during deposition, while the ligands (e.g., hydrogen or halogen) are detached from the silicon motif. Reducing agents may include: mono- and diatomic hydrogen, borane, diborane, alkyboranes (e.g., Me₃B or Et₃B), metals and organometallic compounds among others. In one example, a silicon-containing film is deposited by alternating pulses of F₃SiSiH₂SiH₂CH₃ with atomic hydrogen.

Embodiments of the processes deposit silicon-containing materials on many substrates and surfaces. Substrates on which embodiments of the invention can be useful include, but are not limited to semiconductor wafers, such as crystalline silicon (e.g., Si<100> and Si<111>), silicon on substrate, silicon oxide, silicon germanium, doped or undoped wafers and patterned or non-patterned wafers. Surfaces include wafers, films, layers and materials with dielectric, conductive and barrier properties and include polysilicon, silicon on insulators (SOI), strained and unstrained lattices. Some substrate surface may include glass, such as activated (e.g., Pd) glass substrates. Pretreatment of surfaces includes polishing, etching, activating, reduction, oxidation, hydroxylation, annealing and baking. In one embodiment, wafers are dipped into a 1% HF solution, dried and baked in a hydrogen atmosphere at 800° C.

Embodiments of the processes may be used to grow silicon-containing films with many compositions and properties, including crystalline, amorphous or polysilicon films. Silicon-containing film is the term used herein to describe a variety of product compositions formed by embodiments of the invention. Some silicon-containing films include crystalline or pure silicon, silicon germanium, silicon carbon and silicon germanium carbon. Other silicon-containing films include epi-SiGe, epi-SiGeC, epi-SiC, poly-SiGe, poly-SiGeC, poly-SiC, α-Si, silicon nitride, silicon oxynitride, silicon oxide and metal silicates (e.g., where metals include titanium, zirconium and hafnium). Silicon-containing films include strained or unstrained layers.

Silicon-containing films may include a germanium concentration within the range from about 0 atomic percent to about 95 atomic percent. In other aspects, a germanium concentration is within the range from about 1 atomic percent to about 30 atomic percent. Silicon-containing films may include a carbon concentration within the range from about 0 atomic percent to about 5 atomic percent. In other aspects, a carbon concentration is within the range from about 200 ppm to about 2 atomic percent.

Chlorine and hydrogen incorporation into silicon films has plagued the prior art by the use of lower silanes, lower halosilanes or hexachlorodisilane. Some processes of the invention deposit silicon-containing film that can include impurities, such as hydrogen, halogen and other elements. However, the halogen impurities (e.g., F) occur within the deposited silicon-containing film and are acceptable at less than about 3×10¹⁶ atoms/cm³. Generally, embodiments of the invention may grow silicon-containing films as thick as a single atomic layer, about 2.5 Å, and as thick as about 120 μm, preferably with a thickness in the range from about 2.5 Å to about 10 μm. Various embodiments of the invention teach growing films with a thickness in the range from about 10 Å to about 100 Å, from about 100 Å to about 1,000 Å, from about 1,000 Å to about 1 μm, from about 1 μm to about 4 μm, from about 4 μm to about 50 μm and from about 50 μm to about 120 μm. In other embodiments, film thickness is in the range from about 2.5 Å to about 120 μm, from about 2.5 Å to about 4 μm and from about 2.5 Å to about 100 Å.

The silicon-containing films made by processes of the invention can be doped. In one embodiment, a selective epitaxy silicon layer is doped P type, such as by using diborane to add boron at a concentration in the range from about 10¹⁵ atoms/cm³ to about 10²⁰ atoms/cm³. In another embodiment, a polysilicon layer is doped N⁺ type, such as by ion implanting of phosphorus to a concentration in the range from about 10¹⁹ atoms/cm³ to about 10²¹ atoms/cm³. In another embodiment, a selective epitaxy silicon layer is doped N⁻ type, such as by diffusion of arsenic or phosphorus to a concentration in the range from about 10¹⁵ atoms/cm³ to about 10¹⁹ atoms/cm³.

The silicon-containing films of germanium and/or carbon are produced by various processes of the invention and can have consistent, sporadic or graded elemental concentrations. Graded silicon germanium films are disclosed in commonly assigned U.S. Ser. No. 09/866,172, published as U.S. Pub. No. 2002-0174826, and issued as U.S. Pat. No. 6,770,134 and commonly assigned U.S. Ser. No. 10/014,466, published as U.S. Pub. No. 2002-0174827, and issued as U.S. Pat. No. 6,905,542, which are incorporated herein by reference in entirety for the purpose of describing methods of depositing graded silicon-containing films. In one embodiment, silicon germanium sources (e.g., Cl₃SiSiH₂SiCl₂GeH₃) are used to deposit silicon germanium containing films. In another embodiment, silicon sources (e.g., Cl₃SiSiH₂SiH₂SiH₃) and alternative germanium sources (e.g., GeH₄ or Ge₂H₆) are used to deposit silicon germanium containing films. In this embodiment, the ratio of silicon source and germanium source can be varied in order to provide control of the elemental concentrations while growing graded films.

In another embodiment, silicon carbon sources (e.g., Cl₃SiSiH₂SiH₂CH₃) are used to deposit silicon carbon containing films. In another embodiment, silicon sources (e.g., Cl₃SiSiH₂SiH₂SiH₃) and alternative carbon sources (e.g., C₂H₄) are used to deposit silicon carbon containing films. The ratio of silicon source and carbon source can be varied in order to provide control of the elemental concentration while growing homogenous or graded films.

Furthermore, in another embodiment, silicon carbon sources (e.g., Cl₃SiSiH₂SiH₂GeH₃) and alternative germanium sources (e.g., GeH₄ or Ge₂H₆) are used to deposit silicon germanium carbon containing films. The amounts of silicon carbon source and germanium source can be varied to provide control of the elemental concentrations while growing graded films. In another embodiment, silicon germanium sources (e.g., Cl₃SiSiH₂SiH₂GeH₃) and alternative carbon sources (e.g., C₂H₄) are used to deposit a silicon germanium carbon containing films. The ratio of silicon germanium source and carbon source can be varied to provide control of the elemental concentrations while growing graded films. In other embodiments, silicon germanium carbon containing films are deposited by combining mixtures of silicon sources with silicon germanium sources and/or alternative germanium sources and/or silicon carbon sources and/or alternative carbon sources. Therefore, any silicon compound, silicon source, silicon germanium source, silicon carbon source, alternative silicon source, alternative germanium source and alternative carbon source can be used solely or in combination to deposit silicon-containing films.

Alternative silicon sources may include silanes (e.g., SiH₄) and halogenated silanes (e.g., H_(4−n)SiX_(n), where X is independently F, Cl, Br or I and n=1-4), for example, ClSiH₃, Cl₂SiH₂, Cl₃SiH and Cl₄Si. Alternative germanium sources may include germanes (e.g., GeH₄, Ge₂H₆, Ge₃H₈ or Ge₄H₁₀) and halogenated germanes (e.g., H_(4−n)GeX_(n), where X is independently F, Cl, Br or I and n=1-4). Alternative carbon sources may include alkanes (e.g., CH₄, C₂H₆, C₃H₈, C₄H₁₀), halogenated alkanes (e.g., H_(4−n)CX_(n), where X independently F, Cl, Br or I and n=1-4), alkenes (e.g., C₂H₄) and alkynes (e.g., C₂H₂).

Silicon compounds may be used in various deposition processes of the invention with temperatures in a range from about ambient temperature (e.g., 23° C.) to about 1,200° C. Multiple temperature regions may be controlled throughout the deposition process, such as the process chamber and a delivery line in fluid communication with a precursor source and the process chamber. For example, deposition processes may be conducted with a process chamber at a temperature within the range from about 100° C. to about 1,000° C. while a delivery line has a temperature within the range from about ambient to about 250° C. In other embodiments, the process temperature is less than about 700° C. and is often less than about 500° C. In some embodiments, supplemental reducing agents may be used while depositing a silicon-containing film. In other embodiments, a silicon0containing film is deposited by pyrolysis of the silicon compounds.

In processes of the invention, silicon-containing films are grown by chemical vapor deposition (CVD) processes and include ALE and atomic layer deposition (ALD). Chemical vapor deposition includes the use of many techniques, such as plasma-assisted CVD (PA-CVD), thermal-induced CVD, atomic layer CVD (ALCVD), organometallic or metalorganic CVD (OMCVD or MOCVD), laser-assisted CVD (LA-CVD), ultraviolet CVD (UV-CVD), hot-wire (HWCVD), reduced-pressure CVD (RP-CVD), ultra-high vacuum CVD (UHV-CVD) and others.

In some embodiments of the invention, silicon-containing film may be deposited by ALD. For example, an ALD process is conducted by sequential cycles that include: a pulse of a silicon compound, adsorption of the silicon compound on the substrate or surface, a purge of the reaction chamber, a reduction of the adsorbed silicon compound and a purge of the reaction chamber. Alternatively, when the reduction step includes a reductant pulse, such as atomic hydrogen, the cycle includes: a pulse of a reductant compound, adsorption of the reductant compound on the substrate or surface, a purge of the reaction chamber, a pulse of the silicon compound, reduction of the silicon compound and a purge of the reaction chamber.

The time duration for each silicon compound pulse, the time duration for each reductant pulse and the duration of the purge gas between pulses of the reactants are variable and depend on the volume capacity of a deposition chamber employed, as well as a vacuum system coupled thereto. For example, (1) a lower gas pressure in the chamber will require a longer pulse time; (2) a lower gas flow rate will require a longer time for chamber pressure to rise and stabilize requiring a longer pulse time; and (3) a large-volume chamber will take longer to fill, longer for chamber pressure to stabilize thus requiring a longer pulse time. Similarly, time between each pulse is also variable and depends on volume capacity of the process chamber as well as the vacuum system coupled thereto. In general, the time duration of the silicon compound pulse or the reductant pulse should be long enough for adsorption of the compound. In one example, the silicon compound pulse may still be in the chamber when the reductant pulse enters. In general, the duration of the purge gas should be long enough to prevent the pulses of the silicon compound and the reductant compound from mixing in the reaction zone.

Generally, a pulse time of about 1.0 second or less for a silicon compound and a pulse time of about 1.0 second or less for a reductant are typically sufficient to adsorb alternating amounts of reactants on a substrate or surface. A time of about 1.0 second or less between pulses of the silicon compound and the reductant is typically sufficient for the purge gas to prevent the pulses of the silicon compound and the reductant from mixing in the reaction zone. Of course, a longer pulse time of the reactants may be used to ensure adsorption of the silicon compound and the reductant and a longer time between pulses of the reactants may be used to ensure removal of the reaction by-products.

The processes of the invention may be carried out in equipment known in the art of ALE, CVD and ALD. The apparatus brings the sources into contact with a substrate on which the silicon-containing films are grown. The processes may operate at a range of pressures from about 1 mTorr to about 2,300 Torr depending on specific deposition process and hardware. For example, a silicon-containing film may be deposited by a CVD process with a pressure in the range from about 0.1 Torr to about 760 Torr. In another example, a silicon-containing film may be deposited by an ALD process with a pressure in the range from about 760 Torr to about 1,500 Torr. Hardware that may be used to deposit silicon-containing films includes the Epi CENTURA® system and the POLYGEN™ system available from Applied Materials, Inc., located in Santa Clara, Calif. An ALD apparatus that may be used to deposit silicon-containing films is disclosed in commonly assigned U.S. Ser. No. 10/032,284, published as U.S. Pub. No. 2003-0079686, and issued as U.S. Pat. No. 6,916,398, which is incorporated herein by reference in entirety for the purpose of describing the apparatus. Other apparatuses include batch, high-temperature furnaces, as known in the art.

Another embodiment of the invention teaches methods to synthesize silicon compounds comprising SiRX₆, Si₂RX₆, Si₂RX₈, compounds 1-8 and compounds 9-32, wherein X is independently hydrogen or halogen, R is carbon, silicon or germanium. Disproportionation reactions of non-halogenated, higher silanes are known in the art, such as U.S. Pat. No. 6,027,705, which is incorporated herein by reference in entirety for the purpose of describing the syntheses of silicon compounds. Silanes, halosilanes, germanes, halogermanes, alkyls and haloalkyls may be used as starting materials to form silicon compounds. In some embodiments, silicon compounds may be used as starting materials for other silicon compounds. Starting materials may be made into radical compounds by a variety of methods and include thermal decomposition or plasma excitation. Starting material radicals combine to form silicon compounds. In one example, .SiH₂SiH₃ and .SiCl₂SiCl₃ are respectively made from disilane and hexachlorodisilane and are combined to form H₃SiSiH₂SiCl₂SiCl₃. In another example, .SiH₂SiH₂SiH₃ and .GeCl₃ are respectively made from trisilane and tetrachlorogermane and are combined to form H₃SiSiH₂SiH₂GeCl₃. In another example, .GeH₃ and .SiCl₂SiCl₂SiCl₃ are respectively made from germane and octachlorotrisilane and are combined to form H₃GeSiCl₂SiCl₂SiCl₃. In another example, .CF₃ and .SiH₂SiH₂SiH₃ are respectively made from tetrafluoromethane and trisilane and are combined to form F₃CSiH₂SiH₂SiH₃. In another example, .SiH₂SiH₂SiH₃ and .SiCl₂SiCl₃ are respectively made from trisilane and hexachlorodisilane and are combined to form H₃SiSiH₂SiH₂SiCl₂SiCl₃. In another example, .SiH₂SiH₂SiH₂SiH₃ and .GeCl₃ are respectively made from tetrasilane and tetrachlorogermane and are combined to form H₃SiSiH₂SiH₂SiH₂GeCl₃. In another example, .GeH₃ and .SiCl₂SiCl₂SiCl₂SiCl₃ are respectively made from germane and decachlorotetrasilane and are combined to form H₃GeSiCl₂SiCl₂SiCl₂SiCl₃. In another example, .CF₃ and .SiH₂SiH₂SiH₂SiH₃ are respectively made from tetrafluoromethane and tetrasilane and are combined to form F₃CSiH₂SiH₂SiH₂SiH₃.

Theoretical Experiments 1-17 Including Silicon Compounds SiRX₆

EXAMPLE 1 Monocrystalline Silicon by Selective CVD

A substrate, Si<100>, was employed to investigate selective, monocrystalline film growth by CVD. A silicon oxide feature existed on the surface of the wafer. The wafer was prepared by subjecting to a 0.5% HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 30 sccm of Cl₃SiSiH₃, was delivered to the chamber at 10 Torr and 750° C. The substrate was maintained at 750° C. Deposition was carried out for 3 minutes to form a 400 Å epitaxial layer on the silicon surface, but no epitaxial growth occurred on the silicon dioxide surface.

EXAMPLE 2 Monocrystalline Silicon by Blanket CVD

A substrate, Si<100>, was employed to investigate blanket, monocrystalline film growth by CVD. A silicon oxide feature existed on the surface of the wafer. The wafer was prepared by subjecting to a 0.5% HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 50 sccm of Cl₃SiSiH₃, was added to the chamber at 100 Torr and 650° C. The substrate was maintained at 650° C. Deposition was carried out for 4 minutes to form a 1,600 Å epitaxial layer.

EXAMPLE 3 Polysilicon by CVD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber (POLYGEN™ chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 100 sccm of HF₂SiSiClH₂, was added to the chamber at 80 Torr and 550° C. The substrate was maintained at 550° C. Deposition was carried out for 3 minutes to form a 1,200 Å layer.

EXAMPLE 4 Amorphous Silicon by CVD

A silicon dioxide layered wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 1 minute. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 200 sccm of HCl₂SiSiH₃, was added to the chamber at 200 Torr and 40° C. The substrate was maintained at 40° C. Deposition was carried out for 3 minutes to form a 200 Å layer.

EXAMPLE 5 Silicon Germanium by CVD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 1 minute. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm HCl₂SiGeH₃, was added to the chamber at 100 Torr and 650° C. The substrate was maintained at 650° C. Deposition was carried out for 5 minutes to form a 600 Å epitaxial layer.

EXAMPLE 6 Silicon Carbon by CVD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm of HCl₂CSiH₃, was added to the chamber at 100 Torr and 500° C. The substrate was maintained at 500° C. Deposition was carried out for 15 minutes to form a 1,400 Å epitaxial layer.

EXAMPLE 7 Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm of HCl₂SiGeH₃, was added to the chamber at 100 Torr and 550° C. The silicon compound, H₃CSiH₃, was also added to the chamber at 2 sccm. The substrate was maintained at 550° C. Deposition was carried out for 10 minutes to form a 2,100 Å epitaxial layer.

EXAMPLE 8 Doped Silicon CVD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 100 sccm of Cl₃SiSiH₃, was added to the chamber at 100 Torr and 750° C. The dopant compound, 1 sccm of 1000 ppm B₂H₆ in H₂, was also added to the chamber. The substrate was maintained at 750° C. Deposition was carried out for 3 minutes to form a 600 Å epitaxial doped layer.

EXAMPLE 9 Graded Silicon Germanium by CVD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 50 sccm of HCl₂SiSiH₃, was added to the chamber at 10 Torr and 650° C. A decreasing flow from 225 sccm down to 5 sccm of the silicon compound, HCl₂SiGeH₃, was also added to the chamber during the deposition step. The flow rate was changed non-linearly in respect to time to produce a linearly graded final germanium content in the deposited film. The substrate was maintained at 550° C. Deposition was carried out for 5 minutes to form a 1,200 Å epitaxial layer.

EXAMPLE 10 Graded Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 100 sccm of HCl₂SiCH₃, was added to the chamber at 10 Torr and 650° C. Also, 10 sccm of 5% H₃CSiH₃ was added to the chamber. A decreasing flow from 350 sccm down to 5 sccm of the silicon compound, HCl₂SiGeH₃, was also added to the chamber during the deposition step. The flow rate was changed non-linearly to produce a linearly graded final germanium content in the deposited film. The substrate was maintained at 550° C. Deposition was carried out for 5 minutes to form a 1,300 Å epitaxial layer.

EXAMPLE 11 Monocrystalline Selective Silicon by CVD with Use of HCl

The substrate was prepared as in Example 1. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₃, was added to the chamber at 10 Torr and 600° C. A 5 sccm flow of hydrogen chloride was also delivered to the chamber. The substrate was maintained at 600° C. Deposition was carried out for 8 minutes to form a 500 Å epitaxial layer on the silicon surface, but no epitaxial growth occurred on the silicon dioxide surface.

EXAMPLE 12 Graded Silicon Germanium by ALD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber and subjected to a hydrogen purge for 10 minutes. A flow of carrier gas, argon, was directed towards the substrate and the source compounds were pulsed into this flow. The H-atoms are generated via a tungsten hot-wire. ALD cycle A included: HCl₂SiSiH₃ (0.8 s), purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). ALD cycle B included: HCl₂SiGeH₃ (0.8 s), purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). A graded film is grown by running a sequence of cycles such as: 10A, 1B, 5A, 1B, 1A, 1B, 1A, 5B, 1A, 10B. The substrate was maintained at 300° C. Deposition was carried out for 40 minutes to form a 2,200 Å layer.

EXAMPLE 13 Graded Silicon Germanium Carbon by ALD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber and subjected to a hydrogen purge for 10 minutes. A flow of carrier gas, argon, was directed towards the substrate and the source compounds were pulsed into this flow. ALD cycle included: HCl₂SiCH₃ (0.8 s), purge (1.0 s), HCl₂SiGeH₃ (0.8 s), purge (1.0 s). A film is grown by running cycles for a desired film thickness. The substrate was maintained at 500° C. Deposition was carried out for 40 minutes to form a 2,000 Å layer.

EXAMPLE 14 Synthesis of H₃SiSiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Silane was supplied to reactor 1 at a rate of 15 L/min. Tetrachlorosilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃SiSiCl₃.

EXAMPLE 15 Synthesis of H₃SiGeCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Silane was supplied to reactor 1 at a rate of 15 L/min. Tetrachlorogermane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃SiGeCl₃.

EXAMPLE 16 Synthesis of H₃GeSiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Germane was supplied to reactor 1 at a rate of 15 L/min. Tetrachlorosilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃GeSiCl₃.

EXAMPLE 17 Synthesis of F₃CSiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Tetrafluoromethane was supplied to reactor 1 at a rate of 15 L/min. Tetrachlorosilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including F₃CSiCl₃.

Theoretical Experiments 18-34 Including Silicon Compounds Si₂RX₈

EXAMPLE 18 Monocrystalline Silicon by Selective CVD

A substrate, Si<100>, was employed to investigate selective, monocrystalline film growth by CVD. A silicon oxide feature existed on the surface of the wafer. The wafer was prepared by subjecting to a 0.5% HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 30 sccm of Cl₃SiSiH₂SiH₃, was delivered to the chamber at 10 Torr and 750° C. The substrate was maintained at 750° C. Deposition was carried out for 3 minutes to form a 400 Å epitaxial layer on the silicon surface, but no epitaxial growth occurred on the silicon dioxide surface.

EXAMPLE 19 Monocrystalline Silicon by Blanket CVD

A substrate, Si<100>, was employed to investigate blanket, monocrystalline film growth by CVD. A silicon oxide feature existed on the surface of the wafer. The wafer was prepared by subjecting to a 0.5% HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 50 sccm of Cl₃SiSiH₂SiH₃, was added to the chamber at 100 Torr and 650° C. The substrate was maintained at 650° C. Deposition was carried out for 4 minutes to form a 1,600 Å epitaxial layer.

EXAMPLE 20 Polysilicon by CVD

The substrate was prepared as in Example 19. The wafer was loaded into the deposition chamber (POLYGEN™ chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 100 sccm of HF₂SiSiH₂SiClH₂, was added to the chamber at 80 Torr and 550° C. The substrate was maintained at 550° C. Deposition was carried out for 3 minutes to form a 1,200 Å layer.

EXAMPLE 21 Amorphous Silicon by CVD

A silicon dioxide layered wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 1 minute. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 200 sccm of HCl₂SiSiH₂SiH₃, was added to the chamber at 200 Torr and 40° C. The substrate was maintained at 40° C. Deposition was carried out for 3 minutes to form a 200 Å layer.

EXAMPLE 22 Silicon Germanium by CVD

The substrate was prepared as in Example 19. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 1 minute. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm HCl₂SiSiH₂GeH₃, was added to the chamber at 100 Torr and 650° C. The substrate was maintained at 650° C. Deposition was carried out for 5 minutes to form a 600 Å epitaxial layer.

EXAMPLE 23 Silicon Carbon by CVD

The substrate was prepared as in Example 19. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm of HCl₂CSiH₂SiH₃, was added to the chamber at 100 Torr and 500° C. The substrate was maintained at 500° C. Deposition was carried out for 15 minutes to form a 1,400 Å epitaxial layer.

EXAMPLE 24 Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 19. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₂GeH₃, was added to the chamber at 100 Torr and 550° C. The silicon compound, H₃CSiH₂SiH₃, was also added to the chamber at 2 sccm. The substrate was maintained at 550° C. Deposition was carried out for 10 minutes to form a 2,100 Å epitaxial layer.

EXAMPLE 25 Doped Silicon CVD

The substrate was prepared as in Example 19. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 100 sccm of Cl₃SiSiH₂SiH₃, was added to the chamber at 100 Torr and 750° C. The dopant compound, 1 sccm of 1000 ppm B₂H₆ in H₂, was also added to the chamber. The substrate was maintained at 750° C. Deposition was carried out for 3 minutes to form a 600 Å epitaxial doped layer.

EXAMPLE 26 Graded Silicon Germanium by CVD

The substrate was prepared as in Example 19. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 50 sccm of HCl₂SiSiH₂SiH₃, was added to the chamber at 10 Torr and 650° C. A decreasing flow from 225 sccm down to 5 sccm of the silicon compound, HCl₂SiSiH₂GeH₃, was also added to the chamber during the deposition step. The flow rate was changed non-linearly in respect to time to produce a linearly graded final germanium content in the deposited film. The substrate was maintained at 550° C. Deposition was carried out for 5 minutes to form a 1,200 Å epitaxial layer.

EXAMPLE 27 Graded Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 19. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 100 sccm of HCl₂SiSiH₂CH₃, was added to the chamber at 10 Torr and 650° C. Also, 10 sccm of 5% H₃CSiH₂SiH₃ was added to the chamber. A decreasing flow from 350 sccm down to 5 sccm of the silicon compound, HCl₂SiSiH₂GeH₃, was also added to the chamber during the deposition step. The flow rate was changed non-linearly to produce a linearly graded final germanium content in the deposited film. The substrate was maintained at 550° C. Deposition was carried out for 5 minutes to form a 1,300 Å epitaxial layer.

EXAMPLE 28 Monocrystalline Selective Silicon by CVD with Use of HCl

The substrate was prepared as in Example 18. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₂SiH₃, was added to the chamber at 10 Torr and 600° C. A 5 sccm flow of hydrogen chloride was also delivered to the chamber. The substrate was maintained at 600° C. Deposition was carried out for 8 minutes to form a 500 Å epitaxial layer on the silicon surface, but no epitaxial growth occurred on the silicon dioxide surface.

EXAMPLE 29 Graded Silicon Germanium by ALD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber and subjected to a hydrogen purge for 10 minutes. A flow of carrier gas, argon, was directed towards the substrate and the source compounds were pulsed into this flow. The H-atoms are generated via a tungsten hot-wire. ALD cycle A included: HCl₂SiSiH₂SiH₃ (0.8 s), purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). ALD cycle B included: HCl₂SiSiH₂GeH₃ (0.8 s), purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). A graded film is grown by running a sequence of cycles such as: 10A, 1B, 5A, 1B, 1A, 1B, 1A, 5B, 1A, 10B. The substrate was maintained at 300° C. Deposition was carried out for 40 minutes to form a 2,200 Å layer.

EXAMPLE 30 Graded Silicon Germanium Carbon by ALD

The substrate was prepared as in Example 19. The wafer was loaded into the deposition chamber and subjected to a hydrogen purge for 10 minutes. A flow of carrier gas, argon, was directed towards the substrate and the source compounds were pulsed into this flow. ALD cycle included: HCl₂SiSiH₂CH₃ (0.8 s), purge (1.0 s), HCl₂SiSiH₂GeH₃ (0.8 s), purge (1.0 s). A film is grown by running cycles for a desired film thickness. The substrate was maintained at 500° C. Deposition was carried out for 40 minutes to form a 2,000 Å layer.

EXAMPLE 31 Synthesis of H₃SiSiH₂SiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Disilane was supplied to reactor 1 at a rate of 15 L/min. Tetrachlorosilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃SiSiH₂SiCl₃.

EXAMPLE 32 Synthesis of H₃SiSiH₂GeCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Disilane was supplied to reactor 1 at a rate of 15 L/min. Tetrachlorogermane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃SiSiH₂GeCl₃.

EXAMPLE 33 Synthesis of H₃GeSiCl₂SiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Germane was supplied to reactor 1 at a rate of 15 L/min. Hexachlorodisilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃GeSiCl₂SiCl₃.

EXAMPLE 34 Synthesis of F₃CSiH₂SiH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Tetrafluoromethane was supplied to reactor 1 at a rate of 15 L/min. Disilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including F₃CSiH₂SiH₃.

Theoretical Experiments 35-56 Including Silicon Compounds from Compounds 1-32

EXAMPLE 35 Monocrystalline Silicon by Selective CVD

A substrate, Si<100>, was employed to investigate selective, monocrystalline film growth by CVD. A silicon oxide feature existed on the surface of the wafer. The wafer was prepared by subjecting to a 0.5% HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 30 sccm of Cl₃SiSiH₂SiH₂SiH₃, was delivered to the chamber at 10 Torr and 750° C. The substrate was maintained at 750° C. Deposition was carried out for 3 minutes to form a 400 Å epitaxial layer on the silicon surface, but no epitaxial growth occurred on the silicon dioxide surface.

EXAMPLE 36 Monocrystalline Silicon by Blanket CVD

A substrate, Si<100>, was employed to investigate blanket, monocrystalline film growth by CVD. A silicon oxide feature existed on the surface of the wafer. The wafer was prepared by subjecting to a 0.5% HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 50 sccm of Cl₃SiSiH₂SiH₂SiH₃, was added to the chamber at 100 Torr and 650° C. The substrate was maintained at 650° C. Deposition was carried out for 4 minutes to form a 1,600 Å epitaxial layer.

EXAMPLE 37 Polysilicon by CVD

The substrate was prepared as in Example 36. The wafer was loaded into the deposition chamber (POLYGEN™ chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 100 sccm of HF₂SiSiH₂SiH₂SiH₂SiClH₂, was added to the chamber at 80 Torr and 550° C. The substrate was maintained at 550° C. Deposition was carried out for 3 minutes to form a 1,200 Å layer.

EXAMPLE 38 Amorphous Silicon by CVD

A silicon dioxide layered wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 1 minute. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 200 sccm of HCl₂SiSiH₂SiH₂SiH₂SiH₃, was added to the chamber at 200 Torr and 40° C. The substrate was maintained at 40° C. Deposition was carried out for 3 minutes to form a 200 Å layer.

EXAMPLE 39 Silicon Germanium by CVD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 1 minute. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm HCl₂SiSiH₂SiH₂SiH₂GeH₃, was added to the chamber at 100 Torr and 650° C. The substrate was maintained at 650° C. Deposition was carried out for 5 minutes to form a 600 Å epitaxial layer.

EXAMPLE 40 Silicon Carbon by CVD

The substrate was prepared as in Example 2. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm of HCl₂CSiH₂SiH₂SiH₂SiH₃, was added to the chamber at 100 Torr and 500° C. The substrate was maintained at 500° C. Deposition was carried out for 15 minutes to form a 1,400 Å epitaxial layer.

EXAMPLE 41 Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 36. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₂SiH₂GeH₃, was added to the chamber at 100 Torr and 550° C. The silicon compound, H₃CSiH₂SiH₂SiH₃, was also added to the chamber at 2 sccm. The substrate was maintained at 550° C. Deposition was carried out for 10 minutes to form a 2,100 Å epitaxial layer.

EXAMPLE 42 Doped Silicon CVD

The substrate was prepared as in Example 36. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 100 sccm of Cl₃SiSiH₂SiH₂SiH₃, was added to the chamber at 100 Torr and 750° C. The dopant compound, 1 sccm of 1000 ppm B₂H₆ in H₂, was also added to the chamber. The substrate was maintained at 750° C. Deposition was carried out for 3 minutes to form a 600 Å epitaxial doped layer.

EXAMPLE 43 Graded Silicon Germanium by CVD

The substrate was prepared as in Example 36. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 50 sccm of HCl₂SiSiH₂SiH₂SiH₃, was added to the chamber at 10 Torr and 650° C. A decreasing flow from 225 sccm down to 5 sccm of the silicon compound, HCl₂SiSiH₂GeH₃, was also added to the chamber during the deposition step. The flow rate was changed non-linearly in respect to time to produce a linearly graded final germanium content in the deposited film. The substrate was maintained at 550° C. Deposition was carried out for 5 minutes to form a 1,200 Å epitaxial layer.

EXAMPLE 44 Graded Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 36. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 100 sccm of HCl₂SiSiH₂SiH₂GeH₃, was added to the chamber at 10 Torr and 650° C. Also, 10 sccm of 5% H₃CSiH₂SiH₂SiH₃ was added to the chamber. A decreasing flow from 350 sccm down to 5 sccm of the silicon compound, HCl₂SiSiH₂SiH₂GeH₃, was also added to the chamber during the deposition step. The flow rate was changed non-linearly to produce a linearly graded final germanium content in the deposited film. The substrate was maintained at 550° C. Deposition was carried out for 5 minutes to form a 1,300 Å epitaxial layer.

EXAMPLE 45 Monocrystalline Selective Silicon by CVD with Use of HCl

The substrate was prepared as in Example 35. The wafer was loaded into the deposition chamber (Epi CENTURA® chamber) and subjected to a hydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, was directed towards the substrate and the source compounds were added to the carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₂SiH₂SiH₃, was added to the chamber at 10 Torr and 600° C. A 5 sccm flow of hydrogen chloride was also delivered to the chamber. The substrate was maintained at 600° C. Deposition was carried out for 8 minutes to form a 500 Å epitaxial layer on the silicon surface, but no epitaxial growth occurred on the silicon dioxide surface.

EXAMPLE 46 Graded Silicon Germanium by ALD

The substrate was prepared as in Example 36. The wafer was loaded into the deposition chamber and subjected to a hydrogen purge for 10 minutes. A flow of carrier gas, argon, was directed towards the substrate and the source compounds were pulsed into this flow. The H-atoms are generated via a tungsten hot-wire. ALD cycle A included: HCl₂SiSiH₂SiH₂SiH₃ (0.8 s), purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). ALD cycle B included: HCl₂SiSiH₂SiH₂SiH₂GeH₃ (0.8 s), purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). A graded film is grown by running a sequence of cycles such as: 10A, 1B, 5A, 1B, 1A, 1B, 1A, 5B, 1A, 10B. The substrate was maintained at 300° C. Deposition was carried out for 40 minutes to form a 2,200 Å layer.

EXAMPLE 47 Graded Silicon Germanium Carbon by ALD

The substrate was prepared as in Example 36. The wafer was loaded into the deposition chamber and subjected to a hydrogen purge for 10 minutes. A flow of carrier gas, argon, was directed towards the substrate and the source compounds were pulsed into this flow. ALD cycle included: HCl₂SiSiH₂SiH₂GeH₃ (0.8 s), purge (1.0 s), HCl₂SiSiH₂SiH₂CH₃ (0.8 s), purge (1.0 s). A film is grown by running cycles for a desired film thickness. The substrate was maintained at 500° C. Deposition was carried out for 40 minutes to form a 2,000 Å layer.

EXAMPLE 48 Synthesis of H₃SiSiH₂SiCl₂SiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Disilane was supplied to reactor 1 at a rate of 15 L/min. Hexachlorodisilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃SiSiH₂SiCl₂SiCl₃.

EXAMPLE 49 Synthesis of H₃SiSiH₂SiH₂GeCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Trisilane was supplied to reactor 1 at a rate of 15 L/min. Tetrachlorogermane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃SiSiH₂SiH₂GeCl₃.

EXAMPLE 50 Synthesis of Cl₃SiSiCl₂SiCl₂GeH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Germane was supplied to reactor 1 at a rate of 15 L/min. Octachlorotrisilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including Cl₃SiSiCl₂SiCl₂GeH₃.

EXAMPLE 51 Synthesis of F₃CSiH₂SiH₂SiH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Tetrafluoromethane was supplied to reactor 1 at a rate of 15 L/min. Trisilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including F₃CSiH₂SiH₂SiH₃.

EXAMPLE 52 Synthesis of H₃SiSiH₂SiH₂SiCl₂SiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Trisilane was supplied to reactor 1 at a rate of 15 L/min. Hexachlorodisilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃SiSiH₂SiH₂SiCl₂SiCl₃.

EXAMPLE 53 Synthesis of H₃SiSiH₂SiH₂SiH₂GeCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Tetrasilane was supplied to reactor 1 at a rate of 15 L/min. Tetrachlorogermane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including H₃SiSiH₂SiH₂SiH₂GeCl₃.

EXAMPLE 54 Synthesis of Cl₃SiSiCl₂SiCl₂SiCl₂GeH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Decachlorotetrasilane was supplied to reactor 1 at a rate of 15 L/min. Germane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including Cl₃SiSiCl₂SiCl₂SiCl₂GeH₃.

EXAMPLE 55 Synthesis of F₃CSiH₂SiH₂SiH₂SiH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in the direct series, the inside temperature of reactor 1 was set to 450° C. and the inside temperature of reactor 2 was set to 350° C. The pressure was set to 0.13 MPa. Tetrafluoromethane was supplied to reactor 1 at a rate of 15 L/min. Tetrasilane was supplied to reactor 1 at a rate of 15 L/min. The outlet gas of reactor 2 was analyzed to find that the yields of silane compounds and silicon compounds including F₃CSiH₂SiH₂SiH₂SiH₃.

While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow 

1. A method for depositing a silicon-containing film, comprising: delivering a silicon compound to a surface or a substrate; and reacting the silicon compound to grow the silicon-containing film, wherein the silicon compound comprises one or more compounds having a formula selected from the group consisting of Si₄X₈, Si₄X₁₀, Si₅X₁₀, and Si₅X₁₂, where X is independently a hydrogen or halogen.
 2. The method of claim 1, wherein the silicon compound comprises Si₅X₁₂.
 3. The method of claim 1, wherein X is a hydrogen.
 4. The method of claim 1, wherein X is a halogen.
 5. The method of claim 1, wherein the silicon-containing film is doped.
 6. The method of claim 1, wherein the silicon-containing film has a thickness in a range from about 2.5 Å to about 120 μm.
 7. The method of claim 6, wherein the thickness is about 2.5 Å to about 4 μm.
 8. The method of claim 6, wherein the thickness is about 2.5 Å to about 100 Å.
 9. A method for depositing a silicon-containing film by atomic layer epitaxy, comprising: heating a substrate or a surface to a temperature, and reacting the silicon compound to deposit the silicon-containing film, wherein the silicon compound comprises one or more compounds having a formula selected from the group consisting of Si₄X₈, Si₄X₁₀, Si₅X₁₀, and Si₅X₁₂, where X is independently a hydrogen or halogen.
 10. The method of claim 9, wherein the silicon compound comprises Si₅X₁₂.
 11. The method of claim 9, wherein X is a hydrogen.
 12. The method of claim 9, wherein X is a halogen.
 13. The method of claim 9, wherein the temperature is in a range from about 400° C. to about 800° C.
 14. The method of claim 9, wherein the surface or the substrate is heated to a temperature less than about 500° C.
 15. A method for depositing a silicon-containing film, comprising: delivering a silicon compound to a surface of a substrate; and reacting the silicon compound to grow the silicon-containing film, wherein the silicon compound comprises a compound having the formula:

wherein X₁-X₁₀ are independently hydrogen or halogen, and R is carbon, silicon, or germanium.
 16. The method of claim 15, wherein X₁-X₁₀ are hydrogens.
 17. The method of claim 15, wherein R is silicon.
 18. A method for depositing a silicon-containing film, comprising: delivering a silicon compound to a surface of a substrate; and reacting the silicon compound to grow the silicon-containing film, wherein the silicon compound comprises a compound having the formula:

wherein X₁-X₁₀ are independently hydrogen or halogen, and R is carbon, silicon, or germanium.
 19. The method of claim 18, wherein X₁-X₁₀ are hydrogens.
 20. The method of claim 18, wherein R is silicon.
 21. A method for depositing a silicon-containing film, comprising: delivering a silicon compound to a surface of a substrate; and reacting the silicon compound to grow the silicon-containing film, wherein the silicon compound comprises a compound having the formula:

wherein X₁-X₁₂ are independently hydrogen or halogen, and R is carbon, silicon, or germanium.
 22. The method of claim 21, wherein X₁-X₁₂ are hydrogens.
 23. The method of claim 21, wherein R is silicon. 